Process of treating textiles and textile treating compound



United States Patent O PROCESS OF TREATING TEXTILES AND TEXTILE TREATINGCOMPOUND John Robert Janes, Roslyn Heights, N. Y., assignor, by

mesne assignments, to Deering Milliken Research Corporation, Pendleton,S. C., a corporation of Delaware No Drawing. Application October 1,1951, Serial No. 249,225

11 Claims. 01. 117-65) This invention relates to textile finishingcompounds, to a process of treating cellulosic, proteinaceous and othertextile materials in order to improve their properties, and to theimproved cellulosic, proteinaceous and other textile materials therebyproduced, being a continuation-in-part of my application, Serial Number74,262, now abandoned.

Cellulosic and like textile materials have heretofore been renderedwater repellent by treating them with alkyl silicon halides. Thesecompounds are said to react with hydroxyl groups at the surface of thetextile, forming a chemical bond therewith and splitting out hydrogenhalide. Because of the presence of hydrogen halide, however,considerable care must be exercised in carrying out the process to avoidweakening the cellulosic fabric or otherwise damaging it. It isnecessary, for example, to apply the silicon halide at a low temperatureunder a vacuum or other conditions adapted to carry off hydrogen halideas it is formed. Because of the inconvenience which such precautionsentail, such silicon halides have been limited in their application tothe treatment of woolen goods and like materials which are unaffected byinorganic acids.

Moreover, silicon halides are quite difficclt to handle. They hydrolyzereadily even in the presence of atmospheric moisture to form silicapolymers and hydrogen halides and, thus, must be applied in the absenceof moisture.

Aqueous solutions cannot, of course, be used. The lower members of theseries are corrosive, highly volatile, low boiling liquids, not pleasantto work with in a textile mill.

Now, in accordance with this invention, cellulosic, proteinaceous andother textile materials are treated with quaternary ammonium saltderivatives of silicon compounds. These compounds improve the waterrepellency and/or softness, dimensional stabilization, flame resistanceand crease resistance of the textiles treated therewith. These improvedproperties may result from reaction of the compounds of the inventionwith the textile material at the quaternary ammonium group, giving riseto polymerization of the compound or its decomposition products in situto form a resin. Whatever the explanation for their occurrence, theimproved properties are permanent, and withstand ordinary laundering anddry cleaning procedures.

THE COMPOUNDS OF THE INVENTION They are characterized by the formula:

RnSi[YN(tert)X]4-1t where n is an integer from 1 to 3, R is a saturatedalkyl or aralkyl group preferably containing about 1 to 10 carbon atoms.

Y is a bivalent aliphatic radical preferably of l to about 10 carbonatoms and may, for example, be methylene, propylene, butylene ordecylene. Y cannot be ethylene because of the beta effect discovered bySomer et al., I. A. C. S., 68, 1083 (1946), hereinafter more fullydescribed.

N(tert) is the residue of a tertiary amine. Typical tertiary amineresidues include those in which three nitrogen valences are taken up inone ring, as in pyridine, pyrazine, pyrimidine, quinoline andisoquinoline; those in which two nitrogen valences are taken up in onering, as in piperidine and tetrahydroquinoline and a third taken up withan alkyl group; and those in which three valences are taken up withalkyl groups such as methyl, ethyl, propyl, butyl, pentyl and hexyl,Whether n-, secondary or tertiary. R may, for example, be methyl, ethyl,propyl, butyl, hexyl or decyl. X may be either bromine, chlorine orfluorine.

These compounds may be prepared from the corresponding halogenosilaneand tertiary amine:

N(tert) RnSi(Y-X)4-.. RnSi(YN(tert)X)4 n The halogenosilanes may beprepared as follows: six. 4n(YHMgX) (YH)4-,-SiXn These compounds arewhite or pale-colored solids or viscous liquids, soluble or dispersiblein water, pyridine, dioxane, xylene, mesityl oxide, benzene, chloroform,ethyl alcohol, carbon tetrachloride, ethylene dichloride, ether andacetone.

The quaternary ammonium group of these compounds is decomposed byheating the dry compound above about 90 C., liberating the tertiaryamine and a radical of the form RnSi-Y4-1t. It may also be hydrolyzed bywater at temperatures as low as 60 C. to C., forming these products.

The silicon-carbon linkage is hydrolyzable, but its ease of hydrolysisdepends upon the numbe of carbon atoms of the -Y group attached to thesilicon atom. When Y is methylene, the linkage is hydrolyzed more orless rapidly by dilute alkali or acid at room temperature, and thehydrolysis is exothermic.

During treatment, apparently unrelated reactions may occur, and thesemay proceed concurrently or successively, depending upon the treatmentconditions. The free radical liberated by decomposition of thequaternary ammonium group may polymerize to form a resin, may react Withanother free radical to form a dimer, or react with water to form afatty alcohol. If the reaction is brought about in the presence ofcellulose, it may react with a hydroxyl group of the cellulose moleculeto form an ether of the general structure Where two or more quaternaryammonium groups are present, cross linkages between cellulose moleculesmay be found.

Moreover, if Y is CH2, this ether may also hydrolyze to give the radicalESl-Rll and the ether Cellulose OCH2. The latter may form across-linkage with another cellulose molecule. The RnSi radical maypolymerize to form a silicone resin, a siloxane,

or a silanol, RHSl-OH4-n. If 11:2, the resin will probably be a typicallinear silicone fluid, while if n=1, cross-linking between siliconechains may occur, and a silicone solid will result. Interesting polymersare formed when mixtures of compounds are employed, in which n is 1, 2and 3 (i. e., mixtures where n=1 and 2, or 1 and 3, or 2 and 3). Thepreparation of silicone resins is now well understood, and beyond thescope of this invention. The discussion by Hardy and Megson, QuarterlyReviews,

Cellulose-O C Hs-O H One reaction may occur to the exclusion of theothers. Also, additional reactions not yet understood and not set forthmay be responsible in whole or in part for the improvement in propertiesobtained when the compounds of the invention are applied to textiles.

This reaction takes place with cellulosic materials as a classregardless of their physical form, whether fibers, roving, yarns,fabrics or films; typical natural cellulosic materials including cotton,ilax, jute, hemp, ramie, linen, sisal, bast and wood pulp. Reaction alsooccurs with artificial cellulosic films and fibers, such as regeneratedcellulose, cellulose acetate, cellulose acetate butyrate, cellulosepropionate, cellulose acetate propionate and ethyl cellulose. Apparentlya similar reaction occurs with the protein molecules; the compounds givesimilar results with wool, regenerated keratin, silk, casein, albumen,alginate and like proteinaceous films or fibers, regardless of theirstage of manufacture. They are also useful with synthetic fibers, suchas nylon (i. e., polyamides), Vinyon and Saran polyvinyl resins, Orlonpolyacrylonitrile, and the like.

When the compounds of the invention are applied to cellulosic orproteinaceous textiles, the properties of the textile are modifieddepending upon the particular compound employed and the quantity of thecompound deposited in or on the material. In general, the more compoundemployed, the more intense is the degree of improvement observed.Amounts between about 0.025% and about 20% by the dry weight of thetreated textile are usually sufiicient.

Other finishing agents may be applied to the textile, as is describedbelow.

THE PROCESS OF THE INVENTION In brief, the textile material is treatedwith a solution or dispersion of a compound or mixture of compounds ofthe invention, and then subjected to a treatment adapted to bring aboutchemical reaction between the compound and itself and/or the textilemolecule, i. e., the protein or the cellulose. Towards this end, thematerial may be subjected to an acid or alkali treatment, and/or heatedor baked for a time and at a temperature sufficient to cure it. Thesolvent is wholly or partially removed by heat and/or in a vacuum. Ifdesired, curing may be carried out simultaneously with solvent removalor drying. The cured material may be washed with acid or alkali toremove unreacted material and undesirable by-products of the reaction.

The conditions for carrying out the impregnation depend upon the natureof the material being treated, the compound and the concentration of thetreating solution, and the type of finish desired. The compounds areordinarily employed in the form of an aqueous solution or dispersion. Iftightly woven fabrics are to be treated, it is frequently advantageousto add to the treating solution a small quantity of alcohol, acetone ora wetting agent of the cationic or nonionic type, to assist penetration.Solutions of the compounds in organic liquids such as toluene, benzene,ethyl alcohol, pyridine and ethylene dichloride, which may be anhydrous,if desired, may also be employed.

The concentration of the treating solution depends upon the materialbeing treated and the result desired. Soft finishes which impart only asmall degree of water-repellency and flame resistance are obtained whenthe treating solution contains between about 0.1 and about 0.5% of thecompound, while highly flame retardant, water repellent, soft finishesare obtained when the concentration is between about 0.5 and about 20%compound, depending upon the structure of the compound employed. Thematerial may also be rendered crease resistant and dimensionally stableby use of treating solutions of these concentrations. These figures arebased on a 100% pickup of treating solution by weight of the materialbeing treated. if a lower pickup is obtained, the concentration of thetreating solution should be increased proportionately. This isparticularly true, for example, when tightly woven fabrics are beingtreated.

In order to prevent or minimize loss in tensile strength and tenderingwhen cellulosic materials are treated with the compounds of theinvention, the pH of the treating solution should be adjusted so thatthe cured material has a pH between 5 and 7.5, preferably 6 to 7. The pHof the cured material is considered as equivalent to that of. the waterextract obtained by immersing 20 grams of the cured material in 500 cc.of water for one-half hour. in most cases, it will be found it the pH ofthe treating solution is between 5 and 10, good results will be had.Buffers, which preferably are non-volatile at the curing temperatureused, and inert both to the compounds of the invention and to thetextile material, are employed to maintain the pH of the treatingsolution at the desired value. Bases such as triethanolamine,diethanolamine, sodium acetate, ammonium acetate, pyridine,hexamethylene tetramine and sodium formate, or acids such as lactic,glycolic or alpha hydroxybutanoic acids may be added to adjust the pH ofthe solution.

Other textile finishing agents may be added to the treating solution togive a fuller or stiffer handle to the material. Substances such asammonium acetate, carragheen moss, gum tragacanth, natural resins andwaxes, ammonium stearate or water-soluble cellulose derivatives, such asmethyl, hydroxyethyl and sodium carboxymethyl cellulose, may be added.Other water repellent compounds may be added if desired, provided theydo not diminish the effect of the compounds of the invention. Cationicquaternary ammonium compounds may be employed, for example,octadecyloxymethylpyridinium chloride, N, N-di(chloropyridiniummethyl)paraphenylene di-carbamate, stearamido-methylpyridinium chloride andhexamethylene or decamethylene di(oxymethylpyridinium chloride). Wherethese additional agents are insoluble in water, they are frequentlydispersed in the treating solution by the quaternary ammonium com poundsof the invention, which also have detergent properties.

The treating operation is preferably carried out at temperatures below40 C. if the compounds of the invention are readily decomposed inaqueousor organic solvent solutions or dispersions. More stable compounds maybe applied at more elevated temperatures, in some cases even at theboiling point, but even the most stable compounds tend to hydrolyze whenkept at such temperatures for any extended period of time, and give aless satisfactory finish not as resistant to organic solvents. Ingeneral, therefore, the treating operation is carried out at between 10C. and 40 C.

The treatment is carried out by padding or soaking the material in thetreating solution or dispersion. Conven' tional 2 or 3 roll padders maybe used. The material is preferably subjected to pressure during orafter treatment in order to insure thorough impregnation. Surplus liquoris removed by squeezing or hydroextracting. When the textile material isbeing dimensionally stabilized and/or crease-proofed, an effect obtainedwith certain of the compounds of the invention, it is then stretchedwhile still wet to its original dimensions so that drying and baking maybe carried out while the material is under tension. This stretching stepis unnecessary when the material is merely to be rendered flameretardant and/or water-repellent.

In this connection, it should be noted that the effects of the treatmentare not always entirely fast to severe laundering. For this reason, itis important that the treatment he applied to the fabric in its normal,relaxed state, i. e., its normal dimensions. If treatment and curing arecarried outwith an overstretched fabric, the latter will be stabilizedat its extended size. When the stabilization effect is worn off onlaundering, the fabric will then shrink to its normal relaxed size. Onthe other hand, if the process is carried out on a fabric in its normaldimensions, the gradual loss of finish during laundering will not causeshrinkage.

From this point on, the process followed must take into considerationthe particular compound employed and the finish desired, that is,whether it is desired to decompose the compound at the quaternaryammonium group only, or at both it and the silicon-carbon linkage.

It is not necessary to hydrolyze the silicon-carbon linkage. When it isstable tohydrolysis, permanent waterrepellency, softness, dimensionalstability, crease resistance and flame retardance may be imparted bymerely decomposing the quaternary ammonium group in situ on the textile.In this event the impregnated textile is dried at a temperature lowenough to inhibit decomposition of the quaternary ammonium group (seelater), and then cured.

When it is desired to hydrolyze the silicon-carbon linkage as well, itis possible by suitable steps first to bringv about decomposition of thequaternary mmonium halide group, and then to hydrolyze thesilicon-carbon linkage. In this procedure, the impregnated textile isdried, cured at a temperature between about 80 C. and about 200 C.,impregnated with a solution adapted to hydrolyze the silicon-carbonlinkage, such as dilute aqueous sodium hydroxide, and then warmed at 40C. to 150 C. and cured a second time at temperaturesfrom about 80 C. toabout 250 C. This procedure gives consistently good results with most ofthe compounds of the invention. It does require two impregnation, dryingand two baking steps, however.

Alternatively, both decompositions may be caused to occursimultaneously, or hydrolysis of the silicon-carbon linkage may be madeto occur first. These procedures are quicker and more economical, sincein the latter case the hydrolysis of the silicon-carbon linkage may bemade to occur in the first textile treating bath or directly thereafter,and the subsequent chemical reactions carried nearly to completionbefore the textile is dried, and then completed during the baking step,at which time decomposition of the quaternary ammonium salt also occurs,while in the former case both decompositions are made to occur duringthe first curing step. These procedures have the advantage of requiringonly one impregnation, drying and curmg.

' If the impregnated textile material is heated at temperatures aboveabout 100 C. while still wet, premature decomposition of the quaternaryammonium group may occur. It is usually important that this beprevented, since in many instances no permanent effect may thereafter beobtained. In such cases, it is best to first dry the fabric thoroughlyso that baking and curing may be carried out in the absence of moisture.Thick or tightly woven fabrics especially must be dried with care, forthey tend to retain moisture for a long period of time, even at elevatedtemperatures. The drying temperature is preferably between 30 C. and 80C., but the temperature of drying is less important than the speed andother conditions. If the fabric is dried in more or less stagnant air,as in an oven without artificial circulation, it should not be submittedto a drying temperature of more than 30 C. When, on the other hand, .itis dried in 'a blast of hot air so that the water may be removedrapidly, say in about 3 minutes, then the drying temperature may rise toC. Again, when the treated material is dried on a steam-heated cylinderat C., no permanent effect may be obtained.

The curing or baking temperatures should be between 80 C. and 260 C. Fordecomposition of the quaternary ammonium salt, temperatures between 80C. and C. are preferred, while curing of the silicon-containing reactionproducts may require temperatures up to 50 C. to 100 C. higher; that is,the preferred range in this case lies between 100 C. and 250 C. The timeof baking is inversely proportional to the temperature used, and bothdepend to some extent on the nature of the compound and of the textilematerial. A longer baking time and a relatively low temperature shouldbe used with thick or tightly woven fabrics in order that the heatingmay be uniform throughout, while open weave fabrics or fabrics ofsynthetic fibers, such as nylon, may safely be heated at highertemperatures. If tendering of the material is to be avoided, the time ofbaking is preferably kept as short as possible and the bakingtemperature as low as possible.

In the case of open weave fabrics, if a brisk circulation of air isprovided around and through the material, the preliminary drying stepmay be omitted and the treated material heated at once at the baking orcuring temperature.

The drying operation may be carried out in a covered tenter frame, whilecuring or baking is best carried out on a loom, mat, roll or air laydryer.

Hydrolysis of the silicon-carbon linkage, which is usually accompaniedby polymerization and other chemical interaction of the hydrolysisproducts if n=2 or 1, may be carried out in aqueous neutral, alkaline oracidic media at room or elevated temperatures. It may therefore occurspontaneously in the initial treating solution. Addition of asubstantial amount of a tertiary amine, from 0.5 to 1.5 mols of theamine per mol of the compound, seems to inhibit either the hydrolysis orthe subsequent chemical reactions; upon volatilization of the amine in alater heating step, both reactions proceed as though it had never beenpresent. It may also be carried out after impregnation and/or curingwhile the textile is traveling through a bath of the hydrolyzing media,or while the textile is wet with such a medium or its vapors.

Hydrolysis in neutral or alkaline solution favors formation of linear orcage type polymers, while hydrolysis in acidic media favors formation ofcyclic silicon compounds. Acid hy-drolysis may be objectionable withcellulosic fabrics because tendering may result. It is desirable thatonly the stoichiometric amount of water to form the expected polymer bepresent, but this is not essential, and in fact is a condition almostimpossible to attain after the compound has been applied to the textile.

Hydrolysis may be carried out at from 10 C. to 100 C., depending uponthe case of hydrolysis, as set forth previously. The reaction may beexothermic. Usually it is complete in 15 minutes to an hour, but it mayrequire up to five hours. Solution pH values between about 5 and about10 are preferred, but stronger solutions may be used where no fabricdamage is caused. Bases such as sodium and ammonium hydroxide and acidssuch as hydrochloric or sulfuric are suitable.

.The chemical reactions subsequent to hydrolysis are expedited by highertemperatures, and should also be conducted in the presence of moisture,and/ or an acid or base. Following hydrolysis, and without rinsing,therefore, the treated textile may be warmed while keeping it wet, as ina moist atmosphere, at from 40 C. to 150 C., for from 15 minutes toseveral hours, and then cured at 80 C. to 250 C. for a period of a fewminutes to several hours. Again, possible damage to the fabric governsthe temperature and time employed. The cured fabrics may be washed and/or rinsed, prior to or after final curing, to remove acid or base,by-products and unreacted material.

SYNTHESIS The compounds operable in this invention may be synthesized asfollows, considering, for example, the simplest member of the series,trimethylsilylmethylene pyridinium chloride:

SiCl4+CHsMgBr CHsSiCls CH3SiCl3+SO2Cl2 ClCH2SiCl3 ClCH2SiCi3 3CH3MgBr-(CH3) .sSiCHzCl (CH3 asiCHzCl-i-N (tert) (CH3 asiCHzN (tert) ClSpecifically, to 1.5 mols of silicon tetrachloride dissolved in etherwas added dropwise 1.5 mols of methylmagnesium bromide also dissolved inether, the addition being made in the absence of moisture. After heatingfor 34 hours, the magnesium salts precipitate was filtered out, thefiltrate recovered, and ether removed by distillation.

About 2 mols of methyl trichlorosilane were dissolved in 2 mols ofsulfuryl chloride, a small quantity, i. e., about 0.5 gram, of bcnzoylperoxide added to the solution, and the reactants refluxed for about 8hours. The chloromethyltrichlorosilane was separated by distillation.

This product was reacted, with slight excess of methyl magnesiumbromide, in the manner set forth above, with the exception that thereaction was carried out in the cold. The resulting solution wasfractioned and the tri methylchloromethyl silane recovered.

One moi of trimethylchloromethyl silane was then reacted at atemperature of about 100 C. with 1.2 mols of the tertiary amine, in thiscase pyridine, under anhydrous conditions to prevent prematurehydrolysis. The resulting viscous liquid was trimethylsilylmethylenepyridinium chloride.

By selecting a Grignard reagent the alkyl radical of which has theproper number of carbon atoms, the R and Y groups may be made of thedesired length.

Where the alkyl group of the alkyl trichlorosilane contains 3 or morecarbon atoms, the process is complicated by the fact that all of thepossible chloro-substituted compounds, i. e., t-Cl'llOI'O-, B-chloro-,7-Chl010- and so on, are produced as a result of the reaction withsulfuryl chloride. In all cases, however, that fraction having highestboiling point is the one to be used. If, for example,propyltrichlorosilane is reacted with sulfuryl chloride, otchloro-,B-chloro-, and -chloropropyltrichlorosilane having boiling points of 157C., 162 C. and 173 C., respectively, are obtained. When the mixture isfractionated in a conventional column, the ratio of yields was about1:3.5z3.

As has been mentioned heretofore, it has not been possible to produce bythe above process an organohalogenosilane in which Y has two carbons. Itappears that when the chlorine atom is attached to a carbon atom in aposi tion ,8 to the silicon, the beta CCl bond is just as reactive asthe Si-Cl bond, so that in step 3 of the synthesis, the compound breaksdown into ethylene, evolved as a gas, and the tetra-alkyl silane.

Example 1 T rimethylsilylmethylene pyridinium chloride,

(CH3 3Si-CH2NC5H5C1 is dissolved in water to form a six per centsolution. The pH is adjusted to 8 by addition of a small amount oftriethanolamine. A cotton twill fabric is padded with the solution atroom temperature to a 100% pickup by weight. The treated fabric iswarmed at 60 C. until dry and baked at 120 C. for three minutes. Thefabric is then padded with a 0.3 per cent solution of sodium hydroxide,heated at 40 C. During passage, the temperature of the wet cloth risesspontaneously to 60 C.65 C. Next, the

fabric is removed from the padder and heated in an oven at 60 C. in amoist atmosphere for two hours. It is then dried and cured by heating at150 C. for 15 minutes. Finally, the fabric is washed with a soapsolution, rinsed and dried. The material is water repellent, and alsohas good crease-resistance, dimensional stability and shrinkageresistance.

Example 11 Trimethylsilylpropylene pyridinium chloride,

(CH3)3SiCHECHzC Hg-NCl is dissolved in an aqueous alcohol solution toform an eight per cent solution. A viscose rayon fabric is padded withthis solution to a hundred per cent pickup by weight. The fabric is thenpassed through a bath containing one per cent sodium hydroxide solutionand held at a temperature of C., at a rate such that each section of thecloth remains in the solution for one-half hour. The wet cloth is warmedat C. for another hour in a moist atmosphere to prevent evaporation. Thefabric is dried at 60 C., baked at 140 C. for 15 minutes, and rinsed.The resulting fabric is flame resistant and shows improved waterrepellency, both of which are permanent to wash- Example IIIDimethylsilyldi(methylene pyridinium chloride),

(CH3) 231 C H2-N-C1 is dissolved in a solution containing equal parts ofpyridine and water or ethanol to form a five per cent solution. Thissolution is padded on a wool fabric to a pickup by weight. The fabric isdried at 50 C. and then baked at C. for five minutes. The cured fabricis immersed in a 0.5 ammonium hydroxide solution and traveled slowlythrough the solution so that each portion of the fabric remains in thesolution for one hour. The temperature of the bath is held at 40 C. to50 C. during the treatment. The fabric is then removed from the bath andallowed to remain in a humid oven at a temperature of 60 C. for twohours. The fabric is dried and cured at 175 C. for twenty minutes. Thetreated fabric has improved dimensional stability and is waterrepellent.

A nylon fabric treated in the same way and baked at 205 C. for fiveminutes in the final step likewise has increased water repellency.

Example IV An aqueous treating solution is prepared containing five percent by weight of each of: Diethylsilyldi(methylenc pyridiniumchloride),

(C2H5) 2Si [CH2NC5H5C1] 2 and trimeth ylsilylmcthylene pyridinumchloride,

(CH3 3Si--CH2NC5H5CI An acetate rayon gabardine fabric is padded withthe solution to 100% pickup by weight. The treated fabric is dried at 70C. and then cured at C. for 5 minutes. The cured fabric is immersed in abath containing 0.5% aqueous sodium hydroxide, and warmed at 50 C. forone hour. It is then warmed in a humid atmosphere in an oven at 60 C.for three additional hours and finally dried and cured at C. for 20minutes. The resulting fabric is water repellent, crease resistant anddimensionally stable.

Example V Trimethylsilyldecamethylene pyridinium chloride,

(CH3 3SlC10H20N-C5H5Cl is dissolved in waterto form an eight per centsolution whose pH is adjusted to 8 by addition of triethanolamine. Acotton poplin fabric is padded with this solution to a 100% pickup byweight. The fabric is dried at 60 C. and then baked at 130 C. for 3minutes, and then dried. It is then water-repellent.

Example Vl Dimethylpropylsilylmethylene pyridinium bromide,

C3H7(CHs)2SiCH2N-C5H5Br is dissolved in water to form a 10% solution. Arayon fabric is padded with this solution to a 100% pickup by weight,dried at 70 C. for one hour and then baked at 140 C. for 5 minutes.After rinsing, a sample of the fabric shows good water repellency.

Example VII Six grams of benzylmethylsilyldi(octamethylene pyridiniumchloride),

is dissolved in 94 grams of water to form a six per cent solution byweight. A cotton fabric is padded with this solution to a 100% pickup byweight, dried at 50 C. and then baked at 110 C. for one-half hour. Theproduct obtained is permanently water repellent and also shows a highdegree of dimensional stabilization.

Example VIII Tri-(fi-phenylethyl)silylpropylene pyridinium chloride,

(CsH5CH2CH2) 3Si-CH2CH2CH2NC5H5C1 Example IXDimethylnapthylmethylsilylhexamethylene pyridinium chloride of theformula,

is dissolved in water to form an eight per cent solution by weight. Arayon-cotton gabardine fabric is padded with this solution to a 100%pickup, dried at 80 C., and then baked at 110 C. for 5 minutes. Thecured fabric is padded with a two per cent sodium hydroxide solution at60 C., allowed to remain in the bath for 20 minutes, and then warmed,while still wet, at 60 C. for two hours and finally cured at 160 C. forminutes. The resulting fabric is permanently water repellent anddimensionally stable.

Example X A sufficient quantity of octadecyldimethylsilyldodecamethylenepyridinium fluoride,

C1aH3'z(CH3)2Si-(CH2)12NC5H5F is dissolved in a mixture of equal weightsof pyridine and Water to form a five per cent solution, which is thenapplied to a rayon fabric. The fabric is dried at 55 C. and cured at 150C. for minutes. The cured cloth is rinsed and dried. The product ispermanently water repellent and dimensionally stable.

Example XI A six per cent aqueous solution of dioctadecylsilyldi-(methylene pyridinium chloride),

10 is applied to a cotton fabric using the procedure set forth inExample X. The treated fabric shows excellent water repellency anddimensional stability.

The following is claimed: 1. Compounds having the formula:

RnSi [YN(tert) X] 4-11.

where n is an integer of 1 to 3; R is selected from the group consistingof alkyl and aralkyl radicals; Y is an aliphatic hydrocarbon radicalother than an ethylene radical; X is a halogen selected from the classconsisting of bromine, fluorine and chlorine and N(tert)X represents asubstituent group having no replaceable amine hydrogen and in which thenitrogen has a valence of five.

2. Compounds having the formula:

where n is an integer from 1 to 3; R is an alkylene radical containingfrom 1 to 10 carbon atoms other than an ethylene radical; Y is an alkylradical containing from 1 to 10 carbon atoms; N(tert)X represents asubstituent group having no replaceable amine hydrogen and in which thenitrogen has a valence of five; and X is chlorine.

3. Compounds having the formula:

where n is an integer from 1 to 3 and N(tert) Cl represents asubstituent having no replaceable amine hydrogen and in which thenitrogen has a valence of five.

4. A compound having the formula:

Where n is an integer from 1 to 3; y is an integer from 3 to 10;N(tert)X is a substituent group having no replaceable amine hydrogen andin which the nitrogen has a valence of five and X is chlorine.

5. A compound having the formula:

(CH3 3SiCH2CH2 CH2N (tert) Cl where N(tert)Cl is a substituent grouphaving no replaceable amine hydrogen and in which the nitrogen has avalence of five.

6. A compound having the formula:

(CH3) 3SiCHzN(tert) Br where N(tert)Br is a substituent group having noreplaceable amine hydrogen and in which the nitrogen has a valence offive.

7. A process of treating organic textile materials for the purpose ofimproving the crease resistance, dimensional stability, water repellencyand flame resistance thereof, which comprises impregnating said textilematerial with a compound of claim 2 and subsequently subjecting theimpregnated material to a heat treatment at a temperature within therange from about 40 C. to 250 C., lower than will damage the textile buthigh enough to decompose the compound to form organic silicon-containingresidue and permanently bond said residue to the textile.

8. A process of treating organic textile materials for the purpose ofmodifying the physical characteristics thereof which comprisesimpregnating said material with a compound in accordance with a compoundof claim 1, hydrolyzing the silicon-bridging radical link of saidcompound, and then subjecting said material to a heat treatment atbetween about 40 C. and 250 C.

9. The process for treating organic textile materials in order toimprove the water repellency, dimensional stability, flame resistanceand crease resistance thereof, which comprises impregnating saidmaterial with a solution of the compound of claim 1, drying saidmaterial at a temperature from about 30 C. to C., and subjecting saidimpregnated material to a heat treatment at a temperature of about 80 C.to C. in order to decompose the quaternary ammonium salt while leavingthe SiY linkage intact.

10. The process for treating organic textile materials in order toimprove the characteristics thereof, which comprises impregnating saidmaterial with a solution of the compound of claim 1, drying saidmaterial at a temperature less than 100 C., subjecting said material toa heat treatment at a temperature of about 100 C. to 200 C. to decomposethe quaternary ammonium salt, impregnating said material with ahydrolyzing medium, and then subjecting said material to a second heattreatment at a temperatnre of about 100 C. to 250 C. in order to bondthe reaction product to said material.

11. The process for treating organic textile materials to improve thephysical characteristics thereof which comprises impregnating saidmaterial with a solution of the compound of claim 1, the pH of saidimpregnating solution being at about to 10, maintaining said material ina humid atmosphere at a temperature less than 0, drying said material,and subjecting said material to a heat treatment at a temperature ofabout C. to 250 C.

References Cited in the file of this patent UNITED STATES PATENTS2,419,080 Kraus Apr. 15, 1947 2,516,402 McBee July 25, 1950 2,528,554Rust Nov. 17, 1950 2,557,803 Sommer June 19, 1951 2,580,473 Sowa et a1.Jan. 1, 1952 2,588,365 Dennett Mar. 11, 1952 2,612,482 Rasmussen Sept.30, 1952

1. COMPOUNDS HAVING THE FORMULA:
 9. THE PROCESS FOR TREATING ORGANICTEXTILE MATERIALS IN ORDER TO IMPROVE THE WATER REPELLENCY, DIMENSIONALSTABILITY, FLAME RESISTANCE AND CREASE RESISTANCE THEREOF, WHICHCOMPRISES IMPREGNATING SAID MATERIAL WITH A SOLUTION OF THE COMPOUND OFCLAIM 1, DRYING SAID MATERIAL AT A TEMPERATURE FROM ABOUT 30* C. TO 80*C., AND SUBJECTING SAID IMPREGNATED MATERIAL TO A HEAT TREATMENT AT ATEMPERATURE OF ABOUT 80* C. TO 150* C. IN ORDER TO DECOMPOSE THEQUATERNARY AMMONIUM SALT WHILE LEAVING THE SI-Y LINKAGE INTACT.